This document summarizes a study on the preparation and optical characterization of Cu2+ doped borate glasses. Specifically, it discusses: 1) The preparation of (49.5)B2O3 - 10PbO - 30CdO -10AlF3 glasses doped with 0.5 mol% Cu2+. X-ray diffraction confirmed the amorphous nature of the glasses. 2) Absorption spectroscopy revealed a broad absorption band at 760nm attributed to Cu2+ ions. Excitation spectroscopy showed a band at 389nm due to charge transfer. 3) Emission spectroscopy showed a blue emission peak at 447nm upon excitation at 389nm, attributed to localized excitation

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Spectroscopic Studies on Cu2+
: B2O3 - Cdo - Pbo - AlF3 Glass
K. Nagamuni Reddy*, B. Sudhakar Reddy**
*
(Department of Chemistry, S.V. Degree College, Kadapa-516003, Andhra Pradesh, India)
**
(Department of Physics, S.V. Degree College, Kadapa-516003, Andhra Pradesh, India )
ABSTRACT
This paper reports on the preparation and optical characterization of Cu2+
(0.5 mol %): (49.5)B2O3 - 10PbO -
30CdO -10AlF3 (BPCA)glasses. Due to the homogeneous distribution of Cu2+
ions, the glasses are found to be
in bright blue color has been noticed. From the XRD profile, amorphous nature the glass has been studied.
Triogonal BO3 units transformed into tetrahedral BO4 units has evidenced from the FTIR spectrum of reference
glass. From the measured absorption spectrum of the copper glass exhibits broad absorption band (2
B1g→2
B1g)
at 760 nm have been measured. Emission spectrum of Cu2+
(0.5 mol %): B2O3- CdO – PbO - AlF3 glass has
revealed a blue emission at 447 nm with an excitation wavelength 389 nm.
Keywords - absorption, Cu2+
: glass, emission, excitation, XRD
I. INTRODUCTION
In recent years, a great deal of work has been
carried out on different rare earth (4fn
) ions and also
transition metal (3dn
) ions in crystals and glassy
matrices for various device and optical component
development applications [1-10]. In order to
improvise the glass quality and its optical
performance from B2O3 glasses, suitable quantity
(10mol%) of CdO have been added separately as the
network modifiers[NWF] alongside other property
improving network modifier like AlF3. More
interestingly, we have succeeded in developing these
newly proposed glasses with an excellent
transparency and UV and IR transmission ability. In
order to verify their optical performance, we have
undertaken to examine the optical absorption spectra
of a simple transition metal (Cu2+
) ion with 3d9
as
electronic configuration. Cd belongs to the group IIB
transition elements. The element (Cd) of IIB
transition elements and have significantly improved
the transmission ability and moisture resistance and
transparency in the UV and IR wavelength regions
for their utilization as optical materials of potential
importance with the suitable dopant ions in those
matrices for their applications.Oxide glasses are more
appropriate for practical applications, due to their
high chemical durability and good thermal stability
compared to fluoride, chalcogenide and chloride
glasses. But oxide glasses have a high multiphonon
relaxation rate (1400 cm-1) which causes for the high
non-radiative energy losses that are caused in the
decrement of the emission efficiency in glasses.
Flouride glasses have low multiphonon rates(700cm-
1
) compared to oxide,tellurite or chalcogenide glasses
though they posses low thermal stability. Mixing of
oxide and fluoride ions in the preparation of glasses
will combine the properties of both these ions
i.e.,Oxyflouride glasses will exhibits good thermal
stability, moisture resistance and low multiphonon
rates which have the value in between oxide and
fluoride based glasses for the better emission
efficiency [11-13]. B2O3 is a glass forming oxide,
AlF3 is a conditional glass former and with these two
chemicals in the glass matrix a low rate of
crystallization, moisture resistance, stable and
transparent glasses have been achieved. Transition
metal ions doped glasses have become the subject of
interest due to their potential applications. Bright
blue colour could be found due to the presence of
Cu2+
ions from the point of ligand fields theory.
Recently, Cu2+
ions doped glasses have drawn a great
attention because of their optical bistability [14-17].
Since there are no reports so far with regards to
optical analysis of (49.5) B2O3 - 10PbO-30 CdO -
10AlF3 glass, we have undertaken the present work.
II. EXPERIMENTAL
2.1 GLASS PREPARATION
The borate lead cadmium aluminum fluoride
(BPCA) glasses in the following composition
containing 0.5 mol% Cu2+
ions along with a host
glass.
(i)50B2O3-10PbO-30CdO-10AlF3:Host glass
( ii)(49.5)B2O3-10PbO-30CdO-10AlF3: Cu2+
The starting materials [H3BO3, PbO, CdO, AlF3
and CuO] were purchased from Sigma Aldrich and
employed for subsequent procedures without any
further purification. All the weighed chemicals were
finely powdered and then mixed thoroughly before
each of batches (10g) was melt by using alumina
crucibles in an electric furnace at 9800
C for an hour.
These melts were quenched in between two brass
plates and thus obtained 2-3 cm diameter optical
glasses with a uniform thickness 0.3 cm and these
RESEARCH ARTICLE OPEN ACCESS

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glasses were annealed at 2000
C for an hour in order
to remove thermal strains if any in them soon after
the glasses production.
2.2. MEASUREMENTS
Powder X-ray diffraction (XRD) spectrawere
obtained on a Shimadzu XD3Adiffractometer with a
Ni – filter and CuKα (=1.5418A0
) radiation with an
applied voltage of 30kV and 20mA anode current
calibrated with Si at the rate of 20
/min. The FTIR
spectrum (4000-450 cm-1
) was recorded on aPerkin
Elmer spectrum1 spectrometer with KBr pellets. The
optical absorption spectra(350-1500 nm) for all
glasses were measured on a Varian - Cary win
spectrometer. The excitation and emission spectra
were obtained on a in the wavelength range of 200–
700 nm is recorded using a SHIMADZURF 5301
spectrofluorometer with a slit width of 1.5 mm.
Fig.1a&.1b present the photo graphs of the glasses
studied in the present work.
III. RESULTS AND DISCUSSION
2
D is the free ion term for Cu2+
(d9
). In the
presence of octahedral crystal field it splits into 2
Eg
and 2
T2g with 2
Eg being the lower level. 2
Eg generally
splits due to Jahn –Teller effect. Therefore, Cu2+
is
rarely found in regular octahedral site. Accordingly,
in the present work, Cu2+
is taken to be octahedral co-
ordinated by six oxygen atoms and the octahedron is
tetragonally distorted. Therefore in the tetragonally
distorted octahedral environment, the 2
Eg level splits
into 2
A1 and 2
B1, and 2
T2g levels into 2
E and 2
B2, the
ground state being 2
B1.
The X-ray diffraction spectrum of the 50B2O3 -
10PbO - 30CdO-10AlF3 host (BPCA) glass is given
in Fig.2, which confirms the amorphous nature of the
glass. The UV optical absorption spectrum of
undoped 50B2O3 - 10PbO - 30CdO -10AlF3 (BPCA)
glass is shown in Fig.3, and from this spectrum, it is
also observed that reference glass has shown UV
transmitting ability which is extended up to 330nm.
The FT-IR spectrum of undoped (BPCA) glass is
shown in Fig 4. The structure of borate based glasses
consists of a random network of BO3 triangles with
certain fraction of boroxol (six – membered) rings
[18]. In the infrared spectral region, the vibrational
modes of the borate network have three regions [19-
20]. The 1200-1600cm-1
band is the first region,
which is due to asymmetric stretching relaxation of
the B-O bond of trigonal BO3 units. The second
region is located between 800 -1200 cm-1
and is due
to the B-O bond stretching of tetrahedral BO4 units,
and the last band around 700cm-1
is due to the
bending of B-O-B linkages in the borate network.
Thus, the band around 1340 cm-1
is due to B-O
stretching vibrations of (BO3)3-
unit in metaborate
chain and orthoborates. The peak observed at 987 cm-
1
is attributed to the B-O bond stretching of BO4 units.
The absorption band at 702 cm-1
indicates the B-O-B
bending vibrations. The peak at 457 cm-1
could be
due to lose BO4 units [21]. In general, the IR
absorption band at 806 cm-1
is assigned to the boroxol
ring in the borate glass network. In the present study,
the peak at 806 cm-1
is found missing, which
indicates the absence of boroxol ring in the glass
network. Similarly, the band in the region of 3200-
3600cm-1
is ascribed to the hydroxyl (or) water
groups. Fig.5 presents the Vis-NIR absorption
spectrum of (0.5mol %) Cu2+
doped glass. From this a
broad absorption band near 760nm (2
B1g
2
B2g) is
due to Cu2+
ion in octahedral co-ordination with a
strong tetragonal distortion [22-24]. The optical
absorption studies confirm the presence of Cu2+
ions
in the (49.5) B2O3-10PbO-30CdO-10AlF3:
0.5Cu2+
glasses. Fig.6 reveals the excitation spectrum
of 0.5 mol% CuO doped (49.5) B2O3-10PbO - 30CdO
-10AlF3 glass. According to ligand field theory [35],
oxide based glasses could show charge transfer bands
in the UV region due to the absorption by the oxygen
ligands around the cations.Accordingly, for the 0.5
mol% of CuO doped (49.5) B2O3-10PbO - 30CdO -
10AlF3 glass, one excitation band 389 nm have been
observed. This band is due to charge transfer
phenomena caused by O2-
with an UV radiation
exposure. Fig.6 shows emission spectrum of 0.5
mol% CuO doped (49.5) B2O3-10PbO - 30CdO -
10AlF3 glass with an excitation at 389 nm, and one
emission peak at 447 nm this is due to Cu2+
ions in
the glass. However, according to an earlier report
[36], emission at 447 nm arises due to localized
excitation of isolated Cu2+
ions.
IV. CONCLUSION
It could be concluded that, we have developed
transparent, moisture resistant and more stable optical
glasses based on the chemical composition of (0.5
mol%) Cu2+
: (49.5) B2O3-10PbO-30CdO-10AlF3
.Keeping in view of these encouraging optical
properties, host glasses have been selected to
examine its amorphous nature through XRD
spectrum. Absorption spectrum has revealed the
presence of Cu2+
ions, in the glass investigated.
Emission spectrum of Cu2+
(0.5 mol %): B2O3- CdO
– PbO - AlF3 glass has revealed a blue emission at
447 nm with an excitation wavelength 389 nm. Based
on the spectral results, we suggest that, the Cu2+
glass
have potential applications to carry on further
research work with several other transition metal
ions. Such novel glasses are considered as potential
optical systems. It is strongly contemplated for
further development in future as laser materials
doping with suitable lasing ions.
V. Acknowledgements
This work was financially supported by the
University Grants Commission under Minor

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Research Project Scheme No.F. MRP-
4859/14(SERO/UGC) for distinguished teachers
working in Degree Colleges. In this regard one of the
authors (KNMR) would like to sincerely thank the
Joint Secretary (UGC- SERO, Hyderabad, A.P.,
India.) for his kind co-operation and support for this
present work.
REFERENCES
[1] Cozar O, Ardelean I, Simon V, Ilonca G,
Craciun C, Cefan C. EPR and magnetic
susceptibility investigations of some
Vanadate-Lithium-Borate glasses. J Alloys
Compd 2001;326:124-127.
[2] Kam CH, Buddhudu S. Emission analysis of
Eu3+
: Bi2O3-B2O3-R2O (R = Li, Na, K)
glasses. J Quant Spectrosc Radiat Trans
2004;87:325-337.
[3] Kumar GA, Martinez A, Mejia E, Eden JG.
Fluorescence and up conversion spectral
studies of Ho3+
in alkali bismuth gallate
glasses. J Alloys Compd 2004;365:117-120.
[4] Culea E, Pop L, Simon S. Spectroscopic and
magnetic behaviour of xGd2O3(1-
x)(Bi2O3.PbO) glasses. Mater Sci Engg B
2004;112:59-63.
[5] Yang J, Dai S, Zhou Y, Leiwen, Hu L, Jiang
ZH. Spectroscopic properties and thermal
stability of erbium-doped bismuth –based
glass for optical amplifier. J Appl Phys
2003;93(2):977-983.
[6] Koudelka L, Mosner P, Zeyer M, Jager C.
Lead Borophosphate glasses doped with
Titanium dioxide. J Non-Cryst
Solids 2003;326:72-76.
[7] Balda R, Fernandez J, Depablos A, Fdez
Navarro JM, Arriandiaga MA, Temperature-
dependent concentration quenching and site-
dependent effects of Nd3+
fluorescence in
fluorophosphate glasses. Phys Rev B
1996;53(9):5181-5189.
[8] Lakshminarayana G, Buddhudu S.Spectral
analysis of Cu2+
:B2O3-ZnO-PbO glasses.
Spectrochim Acta Part A 2005;62:364-371.
[9] Souza Filho AG, Mendes Filho J, Melo
FEA, Custódio MCC, Lebullenger R,
Hernandes AC. Optical properties of Sm3+
doped lead fluoroborate glasses. J Phys
Chem Solids 2000;61:1535-1542.
[10] Ardelean I, Peteanu M, Simon V, Cozar O,
Ciorcas F, Lupsor S. Structural and
magnetic properties of CuO-TeO2-B2O3-SrO
glasses. J Magn Magn Mater 1999;253:
196-197.
[11] Garces NY, Wang L, Bai L, Giles NC,
Halliburton LE. Role of copper in the green
luminescence from ZnO crystals. Appl Phys
Lett 2002;81(4):622-624.
[12] Pan A, Ghosh A, A new family of Lead-
Bismuthate glass with a large transmitting
window. J Non-Cryst Solids 2000;271:157-
161.
[13] Fu J, Yatsuda H, New families of glasses
based on Bi2O3. Phys Chem Glasses
1995;36:211-215.
[14] Duran A, Fernandez Navarro JM, Garcia Sol
J, Agullo Lopez F. Study of the coloring
process in copper ruby glass by optical and
ESR spectroscopy. J Material Sci
1984;19:1468-76.
[15] Duran A, Fernandez Navarro JM. The
colouring of glass by Cu2+
ions. Phys Chem
Glasses 1985;26:126.
[16] Kondo Y, Kuroiwa Y, Sugimoto N, Manabe
T, Tokizaki T, Nakamura A. Third-order
optical non-linearities of CuCl-doped
glasses in a near resonance region. J Non-
Cryst Solids 1996;196:90-94.
[17] Asahara Y. Non-linear glass materials.
Ceram Int 1997;23:375.
[18] Ravikumar RVSSN, Komatsu R, Ikeda K,
Chandrasekhar AV, Ramamoorthy L, Reddy
BJ, Reddy YP, Rao PS. Spectroscopic
studies of Copper-doped ARbB4O7 (A =
Na,K) glasses. Phy B 2003;334:398-402.
[19] Krogh Moe J Phys Chem Glasses 1965;6:46.
[20] Kamitsos EI, Karakassides MA, Chryssikos
GD. Vibrational spectra of Magnesium-
Sodium-Borate glasses. Phys Chem Glasses
1987; 91:1073.
[21] Ezz Eldin FM, Alaily NAEL,
“Fundamentals of Glass Science and
Technology” 3rd ESG Conference, 1995.
[22] Lever ABP, Crystal Field Spectra. Inorganic
Electronic Spectroscopy, First ed; Elsevier,
Amsterdam, 1968. p. 249–360.
[23] Figgis BN. Introduction to ligand field
theory. New York; USA: Wiley; 1966.
[24] Qiu J, Miyauchi K, Kawamoto Y, Kitamura
N,Qui J, Hirao K. Long-lasting
phosphorescence in Sn2+
-Cu2+
codoped
Silicate glass and its high pressure treatment
effect. Appl Phys Lett 2002; 81 (3):394-396.
Caption of Figures
Fig.1. Photograph of (a)Host glass and (b) 49.5B2O3-
10PbO-30CdO-10AlF3: 0.5Cu2+
glass
Fig.2. XRD spectrum of 50B2O3-10PbO-30CdO-
10AlF3 glass
Fig.3. UV Absorption transmission spectrum of
50B2O3-10PbO-30CdO-10AlF3 glass
Fig.4. FTIR profile of 50B2O3-10PbO-30CdO-
10AlF3 glass

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ISSN : 2248-9622, Vol. 5, Issue 1( Part 5), January 2015, pp.61-65
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Fig.5.Absorption spectrum of (49.5) B2O3-10PbO-
30CdO-10AlF3: 0.5Cu2+
glass
Fig.6.Excitation spectrum of (49.5) B2O3-10PbO-
30CdO-10AlF3: 0.5Cu2+
glass
Fig.7.Emission spectrum of (49.5) B2O3-10PbO-
30CdO-10AlF3: 0.5Cu2+
glass
(a) Host glass (b) Cu2+
glass
Fig.1.
10 20 30 40 50 60 70 80 90
10
20
30
40
50
60
Intensity(a.u)
Two Theta (in degrees)
Fig.2
300 350 400 450 500 550 600
0
1
2
3
4
Opt.Abs.(Arb.Units)
Wavelength (nm)
Fig.3
Fig.4
600 800 1000 1200
0.6
0.8
1.0
1.2
Absorbance(arb.unitts)
Wavelength (nm)
760 nm
Fig.5
375 380 385 390 395 400
400000
500000
600000
700000
Rel.Exci.Int(arb.unitts)
Wavelength (nm)

emi = 447 nm
389 nm
Fig.6
40.0
60.0
80.0
%T
500.01000.01500.02000.03000.04000.0
1/cm
418.5698.2
962.4
1255.6
1369.4
1508.2
2883.4

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430 440 450 460
800000
900000
1000000
1100000
exci = 389 nm
Rel.Emi.Int(arb.unitts)
Wavelength (nm)
447 nm
Fig.7